Pesticidal N-sulfonyl phosphorodiamido(di)thioates

ABSTRACT

There are disclosed N-sulfonyl phosphorodiamido(di)thioates having pesticidal activity, especially miticidal activity against mites possessing resistance to organophosphorous compounds, when applied to pests or to loci to be freed from the pests by foliar or systematic application techniques.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel N-sulfonyl phosphorodiamido(di)thioatecompounds, to compositions thereof which are useful are pesticides, morespecifically as acaricides, insecticides, and nematocides, and to amethod of controlling pests in agricultural plants. These compounds alsoexhibit fungicidal activity.

2. Description of the Prior Art

Ollinger, U.S. Pat. No. 4,315,870 issued Feb. 16, 1982 disclosesacaricidal, insecticidal and nematicidal phosphorodiamidothioatesrepresented by the formula ##STR1## wherein R¹, R², R³, R⁴, and R⁵ areselected from unsubstituted and substituted alkyl, alkenyl, alkynyl,phenyl, and phenylalkyl groups and X and X¹ are selected from oxygen andsulfur atoms.

Magee, U.S. Pat. No. 3,716,600, discloses insecticidalphosphoroamidothioates represented by the formula ##STR2## wherein R isC₁ -C₃ alkyl; R¹ is C₁ -C₃ alkyl, alkenyl or alkynyl; R² is hydrogen orC₁ -C₃ alkyl; X is carbonyl or sulfonyl; and Y is oxygen or sulfur; whenX is sulfonyl, R³ is C₁ -C₁₀ alkyl, C₃ -C₈ cycloalkyl or phenyl; andwhen X is carbonyl, R³ is hydrogen, C₁ -C₁₈ containing 1-4 halogensselected from F and Cl and Br, C₂ -C₁₈ alkenyl, C₃ -C₁₈ alkynyl, aheterocyclic radical of 1 hetero oxygen, sulfur, or nitrogen atom and 4or 5 annual C atoms and a total of 4 to 8 carbon atoms, C₂ -C₁₂alkoxyalkyl, C₂ -C₁₂ alkylthioalkyl, C₁ -C₁₂ alkoxy, C₁ -C₁₂ alkylthio,pheny, phenyl substituted with 1 or 2 C₁ -C₃ alkyl radicals or C₁ -C₃alkoxy radicals or halogen atoms selected from F and Cl and Br or NO₂groups, styryl, phenyl (C₁ -C₃) alkyl, phenoxy (C₁ -C₃) alkyl,thiophenoxy (C₁ -C₃) alkyl, or phenoxy (C₁ -C₃) alkyl or thiophenoxy (C₁-C₃) alkyl in which the aromatic moiety is substituted with halogensselected from F and Cl and Br or mono-nitro (C₁ -C₃) alkyl.

Kishino et al., U.S. Pat. Nos. 4,134,979 (Jan. 16, 1979) and 4,161,524(July 17, 1979), disclose insecticidal, acaricidal and nematicidalO-alkyl-S-n-propyl-N-sulfonyl-phosphoric acid ester amides representedby the formula ##STR3## wherein R¹ is methyl or ethyl; R² isunsubstituted C₁ -C₆ alkyl or alkenyl, or C₁ -C₆ alkyl substituted byaryl, phenyl, C₁ -C₆ alkylphenyl, or halophenyl; R³ is C₁ -C₆alkylphenyl, C₁ -C₆ alkoxyphenyl, halophenyl, or nitrophenyl; and X is Oor S.

Japanese Patent No. 5 2,128,325 (Derwent Abstract 87 421 Y/49) disclosesinsecticidal, nematocidal and miticidal organic phosphoric acid amideesters represented by the formula ##STR4## wherein R¹ is methyl orethyl; R² is lower alkyl, alkenyl, aralkyl or phenyl substituted with upto three alkyl or halogen groups; R³ is lower alkyl, haloalkyl orphenylalkyl wherein the phenyl ring may be substituted with up to threesubstituents selected from lower alkyl, nitro or lower alkoxy; and X isO or S.

DESCRIPTION OF THE INVENTION

It is an object of the invention to provide compounds, and compositionsthereof, which possess pesticidal, such as insecticidal, acaricidal,nematocidal and miticidal activity, and which are especially activeagainst mites possessing resistance to organo-phosphorous compounds.

It is another object of the invention to provide a method of controllingpests, namely insects, acarids, mites and nematodes.

These and other objects as will become apparent are achieved by thepresent invention which comprises compounds having the formula wherein##STR5## R¹ is unsubstituted or substituted C₁ -C₆ alkyl wherein thesubstituent can be from one to three of the same or different halogensselected from Cl, Br, or F groups;

C₃ -C₈ cycloalkyl;

unsubstituted or substituted phenyl or naphthyl, or can be one to threeof the same or different substituents selected from cyano, nitro, halo,alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, phenoxy,haloalkyl, mono- or di-alkylamino, mono- or di-alkylaminocarbonyl,alkoxy-carbonyl, alkylcarbonyl, alkylcarbonyloxy, phenylthio,phenylsulfinyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl,phenylcarbonyloxy, phenylaminocarbonyl, alkenyloxycarbonyl,alkenylcarbonyloxy, aminocarbonyl, or alkylcarbonylamino and the likewherein the alkyl moiety thereof is a straight or branched chain groupcontaining one to six carbon atoms;

R² is hydrogen;

unsubstituted or substituted C₁ -C₆ alkyl wherein the substituent can bea halo, cyano, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl,alkoxycarbonyloxy, mono- or di-alkylamino, phenoxy or phenylthio groups;

C₃ -C₈ cycloalkyl;

C₃ -C₆ alkenyl;

unsubstituted or substituted phenyl or naphthyl, or unsubstituted orsubstituted phenyl(C₁ -C₅)alkyl, wherein the substituent on the phenylor naphthyl ring can be one to three of the same or differentsubstituents selected from cyano, nitro, halo, alkyl, alkoxy, alkylthio,alkylsulfinyl, alkylsulfonyl, phenoxy, haloalkyl, mono- ordi-alkylamino, mono- or di-alkylaminocarbonyl, alkoxycarbonyl,alkylcarbonyl, alkylcarbonyloxy, phenylthio, phenylsulfinyl,phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl,phenylcarbonyloxyl, phenylaminocarbonyl, alkenyloxycarbonyl,alkenylcabonyloxy, aminocarbonyl, or alkylcarbonylamino and the likewherein the alkyl moiety thereof is a straight or branched chain groupcontaining one to six carbon atoms;

C₃ -C₆ alkynyl;

R³ is hydrogen, methyl or ethyl;

R⁴ is hydrogen, methyl, C₁ -C₆ alkylthio(C₁ -C₂)alkyl, C₁ -C₆ alkoxy(C₁-C₂)alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl;

R⁵ is C₂ -C₆ alkyl; and

X is O or S, preferably O.

More preferred are those compounds of formula I wherein

R¹ is an unsubstituted or substituted C₁ -C₆ alkyl group wherein thesubstituent can be from one to three of the same or different halogensselected from chloro, bromo or fluoro groups;

R² is an unsubstituted or substituted C₁ -C₆ alkyl group wherein thesubstituent can be a cyano, alkoxy, alkylthio, alkylcarbonyl,alkoxycarbonyl, alkylcarbonyloxy, mono- or di-alkylamino, phenoxy orphenylthio group;

a C₃ -C₆ alkenyl group; or

a C₃ -C₆ alkynyl group;

R³ is a methyl group;

R⁴ is hydrogen, methyl, C₃ -C₄ alkenyl;

C₃ -C₄ alkynyl;

R⁵ is C₂ -C₆ alkyl; and

X is O.

These compounds are more preferred because they provide advantageouspesticidal efficacy.

Most preferred are those compounds of formula I wherein

R¹ is an unsubstituted or substituted C₁ -C₆ alkyl group wherein thesubstituent can be one to three of the same or different halogensselected from chloro, bromo or fluoro groups;

R² is an unsubstituted C₁ -C₃ alkyl group;

a C₃ -alkenyl group; or

a C₃ -alkynyl group;

R³ is methyl;

R⁴ is hydrogen;

R⁵ is 1-methylpropyl; and

X is O.

These compounds are most preferred because they provide especiallyadvantageous pesticidal efficacy.

In another aspect, the invention comprises a pesticidal compositioncomprising a pesticidally effective amount of the compound of formula Iand an agronomically acceptable carrier.

In yet another aspect, the invention comprises a method of controllingpests comprising applying to the pests or to the loci of plants to befreed from infestation by the pests a pesticidally effective amount ofthe compound of formula 1.

As used in the specification and claims, the terms "alkyl", "alkenyl",and "alkynyl" are meant to include both branched and straight chainalkyl, alkenyl, and alkynyl groups. Representative examples of suchgroups include methyl, ethyl, propyl, isopropyl, sec-butyl, isobutyl,tert-butyl, pentyl, neopentyl, hexyl, allyl, 2-butenyl,3-methyl-1-pentenyl, 3-hexenyl, propynyl, 1-pentynyl,4-methyl-1-pentynyl, hexynyl, and the like.

By "alkenyl" group, as used in the specification and the claims, ismeant an alkenyl group such as an allyl group, or the like, with one cisor trans double bond.

By "alkynyl" group, as used in the specification and the claims, ismeant an alkynyl group, such as a propargyl group, with one triple bond.

By a substituted phenyl(C₁ -C₅)alkyl group is meant a phenyl(C₁-C₅)alkyl group, e.g., benzyl, phenethyl, 3-phenyl-1-methylpropyl, etc.,the phenyl ring of which is substituted with one or more, but preferablywith one to three substituents selected from the group of substituentsdefined for substituted phenyl above.

Representative compounds of the invention include those compounds listedbelow:

N-Methanesulfonyl N,N'-dimethyl S-pentyl phosphorodiamidothioate

S-Ethyl N-hexanesulfonyl N-hexyl phosphorodiamidothioate

N-Cyclopropanesulfonyl N-(2-methoxyphenyl) N'-methyl S-propylphosphorodiamidothioate

N-(4-Bromophenyl) N-cyclohexanesulfonyl N'-ethyl S-hexylphosphorodiamidothioate

N'-Methyl S-pentyl N-phenylsulfonyl N-phenyl phosphorodiamidothioate

N-(4-Chlorophenyl)sulfonyl N-cyclopropyl S-ethyl N'-(2-propenyl)phosphorodiamidothioate

N-Benzylsulfonyl N-cyclohexyl N'-(2-propynyl) S-propylphosphorodiamidothioate

N-(4-Bromobenzyl)sulfonyl N-methyl S-pentyl N'-(2-propenyl)phosphorodiamidothioate

N-Cyanoethyl N'-ethyl N-phenylsulfonyl S-propyl phosphorodiamidothioate

N-(1-Ethoxyhexyl) N'-methyl N-(4-nitrophenylsulfonyl) S-pentylphosphorodiamidothioate

N'-Methyl S-(1-methylpropyl) N-(2-methylthioethyl )N-trifluoromethanesulfonyl phosphorodiamidothiaote

N-(3-Chlorohexyl)sulfonyl N-(2-methoxycarbonyl)hexyl N'-methylS-(1-methylpropyl) phosphorodiamidothioate

N-(Ethoxycarbonyl)methyl N'-ethyl S-propyl N-trichloromethanesulfonylphosphorodiamidothioate

N-(4-Bromohexane)sulfonyl N'-methyl S-(1-methylpropyl)N-(4-phenoxyhexyl) phosphorodiamidothioate

S-Butyl N-(3-hexynyl) N'-methyl N-trichloromethanesulfonylphosphorodiamidothioate

S-(1-Methylethyl) N-(2-propynyl) N'-methyl N-trifluoromethanesulfonylphosphorodiamidothioate

N-(2-Hexenyl) N'-methyl S-(1-methylpropyl) N-trifluoromethanesulfonylphosphorodiamidothioate

N-(3-Chloropropyl)sulfonyl N-hexyl S-(2-methylpropyl) N'-(2-propenyl)phosphorodiamidothioate

N-(3-Chloropropyl)sulfonyl N,N'-dimethyl S-propylphosphorodiamidothioate

N-Methanesulfonyl N,N'-dimethyl S-(1-methylpropyl)phosphorodiamidodithioate

S-Butyl N-hexanesulfonyl N-(2-methoxyethyl) N'-methylphosphorodiamidodithioate

N-Cyclopropanesulfonyl N,N'-dimethyl S-hexyl phosphorodiamidothioate

N-(4-Bromophenylsulfonyl) N-ethyl S-propyl phosphorodiamidodithioate

N'-Methyl S-(2-methylpropyl) N-(2-methylthioethyl)N-trifluoromethanesulfonyl phosphorodiamidodithioate

N'-Ethyl N-(2-propenyl) S-propyl N-trichloromethylsulfonylphosphorodiamidothioate

S-(1-Methylpropyl) N-phenylsulfonyl N-(2-propynyl)phosphorodiamidodithioate

N-Butanesulfonyl N-(3-hexynyl) S-(2-methylpropyl) N'-(2-propenyl)phosphorodiamidodithioate

N-Ethyl N-ethanesulfonyl N'-methyl S-(2-methylpropyl)phosphorodiamidodithioate

N-Butyl N-butanesulfonyl N',S-diethyl phosphorodiamidodithioate

N-Butanesulfonyl N-(6-cyanohexyl) N'-methyl S-(1-methylethyl)phosphorodiamidodithioate

N-(3-Methylpentyl) N-phenylsulfonyl N'-(2-propynyl) S-propylphosphorodiamidothioate

N-(3-Methylethyl)sulfonyl N-(2-methylpropyl) S-pentyl N-(2-propenyl)phosphorodiamidodithioate

N-(2-Ethoxyethyl) N-(2-ethylbutanesulfonyl) N'-methyl S-(1-methylpropyl)phosphorodiamidodithioate.

Especially preferred embodiments embraced by the invention are:

N-methanesulfonyl N,N'-dimethyl S-(1-methylpropyl)phosphorodiamidothioate

N,N'-dimethyl N-(4-methylphenylsulfonyl) S-(1-methylpropyl)phosphorodiamidothioate

N-methanesulfonyl N,N'-dimethyl S-(1-methylpropyl) N'-(2-propenyl)phosphorodiamidothioate

N-ethyl N-methanesulfonyl N'-methyl S-(1-methylpropyl) N'-(2-propenyl)phosphorodiamidothioate

N-methanesulfonyl N'-methyl S-(1-methylpropyl) N-methylthioethylphosphorodiamidothioate

N-methanesulfonyl N'-methyl S-(1-methylpropyl) N-(2-propynyl)phosphorodiamidothioate

N,N'-dimethyl S-(1-methylpropyl) N-trifluoromethanesulfonylphosphorodiamidothioate

N-butanesulfonyl N,N'-dimethyl S-(1-methylpropyl)phosphorodiamidothioate

The compounds of the invention can be synthesized, as is outlined in thesequence of reaction equations below, by reaction, carried out generallyin the presence of an inert solvent, such as tetrahydrofuran (THF),chlorinated hydrocarbons, aromatic hydrocarbons, and ethers, at roomtemperature and atmospheric pressure, of a phosphorodichloridothioate(3) with a sodium salt of a sulfonamide (2) to form monochloride (4).Reaction, carried out generally in the presence of an inert solvent suchas THF at room temperature and atmospheric pressure, of (4) with anamine in the presence of an acid scavenger, for example, excess amine,yields diamidate (I). The sodium salt (2) is formed by reaction, carriedout generally in the presence of an inert solvent such as THF at roomtemperature and atmospheric pressure, of a sulfonamide (1) with a strongbase, for example, sodium hydride or sodium hydroxide. ##STR6##

The preparation of phosphorodichloridothioates such as compound (3)above is described in Hurt, U.S. Pat. No. 4,056,581.

The compounds of the invention are useful for the protection of plantsand animals, including mammals, from the ravages of harmful and annoyingpests. These compounds are particularly effective against arthropods (invarying stages of development) and are especially effective againstmembers of the Class Arachnoidea, which includes the Order Acarina, asrepresented by mites and ticks, and the Class Insecta, the insects.Among the arthropods which are effectively controlled by the compoundsof the present invention are the chewing insects, e.g., the southernarmyworm (Spodoptera eridania), mites, e.g., the two-spotted spider mite(Tetranychus urticae) and others.

The compounds of this invention are also active as fungicides.

Furthermore, compounds of this invention possess nematocidal activity.Among the nematodes which are effectively controlled by the compounds ofthe present invention are soil nematodes, typified by the southern rootknot nematode (Meloidogyne incognita).

Generally, control of pests is achieved in accordance with thisinvention by application of the compounds in pesticidally effectiveamounts (e.g., arthropodicidally effective amounts) either directly tothe pests to be controlled or to the loci to be freed of or protectedfrom attack by such pests. Plant protection loci may be defined as theaerial and subterranean portions of plants or propagative subunits andtheir immediate or future environs. For example, food, fiber, forage,forest, and ornamental crops and stored products thereof represent plantprotection loci. Treatment with compounds of this invention of domesticanimals, and their immediate environs similarly constituterepresentative loci for protection against various annoyingectoparasitic or endoparasitic Acarina (Acari) and Insecta. Many of theformulations listed below can be utilized on animals in the control ofparasites. Thus, the compounds can be deposited on or in the soil,plants, insects, manmade structures, or other substrates as deposits,coatings, etc. Accordingly, compounds of the present invention provideutility as the essential active ingredient of pesticidal compositionssuitable for agricultural and sanitary purposes.

The term "control" as employed in the specification and claims of thisapplication is to be construed as any means which adversely affects theexistence or growth of a living organism. Such means can comprise acomplete killing action, eradication, arresting in growth, inhibition,reduction in number or any combination thereof.

The term "pest" as employed in the specification and claims of thisapplication refers to fungi, nematodes and various arthropods especiallyinsects and acarids.

The phosphorodiamidothioates of this invention possess general utilityas arthropodicites, particularly as against members of the classArachnoidea, which includes the order Acarina, as represented by mitesand ticks, and Insecta, the insects. Certain compounds of this inventionare also active as nematocides and fungicides, particularly fungicides.

For use as pesticides, the compounds of this invention can be used assolutions in organic solvents or formulations. For example, they can beformulated as wettable powders, emulsifiable concentrates, dusts,granular formulations or flowable emulsifiable concentrates. In suchformulations, the phosphorodiamidothioates are extended with anagronomically acceptable liquid or solid carrier and, when desired,suitable surfactants are likewise incorporated. Surfactants commonlyused in the art can be found in the John W. McCutcheon, Inc. publication"Detergents and Emulsifiers Annual".

The phosphorodiamidothioates can be taken up or mixed with a finelyparticled solid carrier, as for example, clays, inorganic silicates,carbonates, and silicas. Organic carriers can also be employed. Dustconcentrates are commonly made wherein phosphorodiamidothioates arepresent in the range of about 20 to about 80%. For ultimateapplications, these concentrates are normally extended with additionalsolid to give an active ingredient content of from about 1 to about 20%.Granular formulations are made using a granular or pelletized form ofcarrier, such as granular clays, vermiculite, charcoal or corn cobs, andcan contain the active ingredient in from about 1 to about 25% byweight.

Wettable powder formulations are made by incorporating the compounds ofthis invention in an inert, finely divided solid carrier along with asurfactant which can be one or more emulsifying, wetting, dispersing orspreading agents or blend of these. The phosphorodiamidothioates areusually present in the range of about 10 to about 35% by weight andsurfactants from about 0.5 to about 10% by weight.

One convenient method for preparing a solid formulation is to impregnatethe phosphorodiamidothioate onto the solid carrier by means of avolatile solvent such as acetone. In this manner, adjuvants, such asactivators, adhesives, plant nutrients, synergists and varioussurfactants can also be incorporated.

Emulsifiable concentrate formulations can be prepared by dissolving thephosphoramidothioates of this invention in an agronomically acceptableorganic solvent and adding a solvent-soluble emulsifying agent. Suitablesolvents are usually water-immiscible and can be found in thehydrocarbon, ketone, ester, alcohol and amide groups of organicsolvents. Mixtures of solvents are commonly employed. The surfactantsuseful as emulsifying agents can constitute about 0.5 to about 10% byweight of emulsifiable concentrate and can be anionic, cationic ornon-ionic in character. The concentration of the active ingredients canvary from about 20 to about 50% by weight.

For use as pesticidal agents, these compounds should be applied in aneffective amount sufficient to exert the desired pesticidal activity bytechniques well known in the art. Usually, this will involve theapplication of the phosphorodiamidothioate to the loci to be protectedfrom or freed of pests in an effective amount when incorporated in anagronomically acceptable carrier. However, in certain situations, it maybe desirable and advantageous to apply the compounds directly onto theloci to be protected from or freed of pests without the benefit of anysubstantial amount of carrier. This is a particularly effective methodwhen the physical nature of the toxicants is such as to permit what isknown as "low-volume" application, that is, when the compounds are inliquid form or substantially soluble in higher boiling solvents.

The application rate will, of course, vary depending upon the purposefor such application, the phosphorodiamidothioate being utilized, thefrequency of dissemination and the like.

By "agronomically acceptable carrier" is meant any substance which canbe utilized to dissolve, disperse, or diffuse the chemical incorporatedtherein without impairing the effectiveness of the toxic agent and whichdoes no permanent damage to such environment as soil, equipment andagronomic crops.

For use as insecticides and acaricides, dilute sprays can be applied atconcentrations of about 0.01 to about 20 pounds of thephosphorodiamidothioate ingredient per 100 gallons of spray. They areusually applied at about 0.1 to about 5 pounds per 100 gallons. In moreconcentrated sprays, the active ingredient is increased by a factor ofabout 2 to about 12. With dilute sprays, applications are usually madeto the plants until run off is achieved, whereas with more concentratedlow-volume sprays, the materials are applied as mists.

For use as a fungicide, the compounds of this invention can be appliedas fungicidal sprays by methods commonly employed, such as, conventionalhigh-gallonage hydraulic sprays, low-gallonage sprays, air-blast sprays,aerial sprays and dusts. The dilution and rate of application willdepend upon the type of equipment employed, the method of applicationand diseases to be controlled, but the preferred effective amount isusually about 0.1 lb. to about 50 lbs. per acre of the activeingredient.

As a fungicidal seed protectant, the amount of toxicant coated on theseed is usually at a dosage rate of about 0.1 to about 20 ounces perhundred pounds of seed. As a soil fungicide the chemical can beincorporated in the soil or applied to the surface usually at a rate ofabout 0.1 to about 50 lbs. per acre. As a foliar fungicide, the toxicantis usually applied to growing plants at a rate of about 0.25 to about 10lbs. per acre.

For use as a nematocide, systemic agent, or as a soil insecticide, thephosphorodiamidothioates can be applied as a solid formulation,preferably a granular formulation or as a diluted liquid preparation, bybroadcasting, sidedressing soil incorporation or seed treatment.

The composition can also be added to transplant or irrigation water orto units employed in propagation, such as seeds, tubers, roots,seedlings, etc., so as to disinfect and/or provide residual protectionfrom nematodes, soil insects (and mites) and via systemic uptake, foliarpests. The application rate can be from about 0.5 to about 50 pounds peracre; however, higher rates can also be used. The preferred rate is fromabout 1 to about 25 pounds per acre. For soil incorporation, thecompounds of this invention can be mixed with the soil or other growthmedium at a rate of about 1 to about 100 ppm of active ingredient.

The compounds of this invention can be utilized as the sole pesticidalagents or they can be employed in conjunction with other bactericides,fungicides, herbicides, insecticides, acaricides, nematocides andcomparable pesticides.

The following examples are presented to illustrate but a few embodimentsof the invention and are not to be construed as limiting in scope. Allparts and percentages are by weight unless otherwise indicated.

EXAMPLE 1

N-Methanesulfonyl N,N'-dimethyl S-(1-methylpropyl)phosphorodiamidothioate

Sodium hydride (0.6 g., 0.024 mole) and methyl methanesulfonamide (2.7g., 0.025 mole) were stirred in 20 ml. of tetrahydrofuran (THF) at roomtemperature for about 24 hours to produce the sodium salt of methylmethanesulfonamide. A solution of S-(1-methylpropyl)phosphorodichloridothioate (5 g., 0.024 mole) in 20 ml. of THF was addedall at once to the reaction product mixture from above, and theresulting mixture was stirred 4 hours at ambient temperature to produceN-methanesulfonyl N-methyl S-(1-methylpropyl)phosphoroamidochloridothioate. A solution of methylamine (1.55 g., 0.05mole) in 10 ml. of THF was added to the reaction product mixture fromabove, and the resulting mixture was stirred 2 hours at ambienttemperature, diluted with 250 ml. of ether, filtered through superceland evaporated to afford 6.1 g. of product as a brown oil.

The following compounds were prepared by following substantially theprocedure set forth in Example 1.

EXAMPLE 2

N,N'-Dimethyl N-(4-Methylphenylsulfonyl) S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 3

N-Methanesulfonyl N,N'-Dimethyl S-(1-Methylpropyl) N'-(2-Propenyl)Phosphorodiamidothioate

EXAMPLE 4

N-Ethyl N-Methanesulfonyl N'-Methyl S'-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 5

N-Methanesulfonyl N'-Methyl S-(1-Methylpropyl) N-MethylthioethylPhosphorodiamidothioate

EXAMPLE 6

N-Methanesulfonyl N'-Methyl S-(1-Methylpropyl) N-(2-Propynyl)Phosphorodiamidothioate

EXAMPLE 7

N,N'-Dimethyl S-(1-Methylpropyl) N-TrifluoromethanesulfonylPhosphorodiamidothioate

EXAMPLE 8

N-Butanesulfonyl N,N'-Dimethyl S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 9

N-Methanesulfonyl N-Methyl S-(1-Methylpropyl) Phosphorodiamidothioate

EXAMPLE 10

N,N'-Dimethyl S-(1-Methylpropyl) N-PhenylsulfonylPhosphorodiamidothioate

EXAMPLE 11

N-Ethanesulfonyl N,N'-Dimethyl S-(1-Methylethyl) Phosphorodiamidothioate

EXAMPLE 12

N,N'-Dimethyl S-(1-Methylpropyl) N-(4-Nitrophenyl)sulfonylPhosphorodiamidothioate

EXAMPLE 13

N-Methanesulfonyl N,N'-Dimethyl S-(1-Methylpropyl) N-(2-Propenyl)Phosphorodiamidothioate

EXAMPLE 14

N'-Ethyl N-Methanesulfonyl N-Methyl S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 15

N-Methanesulfonyl N'-Methyl S-(1-Methylpropyl) N-PhenylPhosphorodiamidothioate

EXAMPLE 16

N-Benzyl N-Methanesulfonyl N'-Methyl S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 17

N-Methanesulfonyl N-(2-Methoxyethyl) N'-Methyl S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 18

N-Cyclohexyl N-Methanesulfonyl N'-Methyl S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 19

N,N'-Dimethyl N-(1-Methylethylsulfonyl) S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 20

N-(4-Methoxyphenyl)sulfonyl N,N'-Dimethyl S-(1-Methylpropyl)Phosphorodiamidothioate

EXAMPLE 21

N-Methanesulfonyl N,N'-Dimethyl S-(1-Methylpropyl) N-MethylthiomethylPhosphorodiamidothioate

Table I below lists the Examples, 1-21, and sets forth the substituentscorresponding to the designations, X, R¹, R², R³, R⁴, and R⁵ in thestructural formula I.

The analytical data, namely, elemental analysis data and nuclearmagnetic resonance data, for the examples are set forth in Tables II andIII, respectively, below.

                                      TABLE I                                     __________________________________________________________________________     ##STR7##                                                                     Ex. No.                                                                            X R.sup.1  R.sup.2  R.sup.3                                                                            R.sup.4  R.sup.5                                __________________________________________________________________________    1    O CH.sub.3 CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3                                                 (1-Methylpropyl)                       2    O 4-CH.sub.3C.sub.6 H.sub.4                                                              CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          3    O CH.sub.3 CH.sub.3 CH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                                                    CH(CH.sub.3)CH.sub.2 CH.sub.3          4    O CH.sub.3 CH.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          5    O CH.sub.3 CH.sub.3 SCH.sub.2 CH.sub.2                                                            CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          6    O CH.sub.3 CH.sub.2CCH                                                                            CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          7    O CF.sub.3 CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          8    O C.sub.4 H.sub.9n                                                                       CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          9    O CH.sub.3 CH.sub.3 H    H        CH(CH.sub.3)CH.sub.2 CH.sub.3          10   O C.sub.6 H.sub.5                                                                        CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          11   O C.sub.2 H.sub.5                                                                        CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          12   O 4-NO.sub.2C.sub.6 H.sub.4                                                              CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          13   O CH.sub.3 CH.sub.3 CH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                                                    CH(CH.sub.3)CH.sub.2 CH.sub.3          14   O CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                                    H        CH(CH.sub.3)CH.sub.2 CH.sub.3          15   O CH.sub.3 C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          16   O CH.sub.3 CH.sub.2 C.sub.6 H.sub.5                                                               CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          17   O CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3                                                            CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          18   O CH.sub.3 c-C.sub.6 H.sub.11                                                                     CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          19   O CH(CH.sub.3).sub.2                                                                     CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          20   O 4-CH.sub.3 OC.sub.6 H.sub.4                                                            CH.sub.3 CH.sub.3                                                                           H        CH(CH.sub.3)CH.sub.2 CH.sub.3          21   O CH.sub.3 CH.sub.3 CH.sub.3                                                                           CH.sub.2SCH.sub.3                                                                      CH(CH.sub.2)CH.sub.2 CH.sub.3          __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                        Elemental Analyses                                                            Ex.               Elemental Analysis Calcd. (Found)                           No.  Emp. Formula   C         H     N                                         ______________________________________                                        1    C.sub.7 H.sub.19 N.sub.2 O.sub.3 PS.sub.2                                                  30.65 (30.75) 6.93 (7.29)                                                                     10.22 (9.96)                                2    C.sub.13 H.sub.23 N.sub.2 O.sub.3 PS.sub.2                                                 44.56 (43.25) 6.61 (6.71)                                                                     8.00 (7.36)                                 3    C.sub.10 H.sub.23 N.sub.2 O.sub.3 PS.sub.2                                                 38.22 (37.93) 7.32 (7.53)                                                                     8.92 (8.96)                                 4    C.sub.8 H.sub.21 N.sub.2 O.sub.3 PS.sub.2                                                  33.33 (32.93) 7.29 (7.62)                                                                     9.72 (8.58)                                 5    C.sub.9 H.sub.23 N.sub.2 O.sub.3 PS.sub.3                                                  35.76 (33.92) 7.62 (7.53)                                                                     9.27 (8.25)                                 6    C.sub.9 H.sub.19 N.sub.2 O.sub.3 PS.sub.2                                                  36.24 (35.70) 6.37 (6.30)                                                                     9.39 (9.01)                                 7    C.sub.7 H.sub.16 F.sub.3 N.sub.2 O.sub.3 PS.sub.2                                          25.61 (24.80) 4.88 (4.73)                                                                     8.54 (8.17)                                 8    C.sub.10 H.sub.25 N.sub.2 O.sub.3 PS.sub.2                                                 42.10 (39.70) 8.77 (8.12)                                                                     9.82 (7.87)                                 9    C.sub.6 H.sub.17 N.sub.2 O.sub.3 PS.sub.2                                                  27.70 (27.64) 6.54 (6.58)                                                                     10.77 (10.51)                               10   C.sub.12 H.sub.21 N.sub.2 O.sub.3 PS.sub.2                                                 42.86 (43.15) 6.25 (6.34)                                                                     8.33 (8.36)                                 11   C.sub.8 H.sub.21 N.sub.2 O.sub.3 PS.sub.2                                                  33.33 (32.97) 7.29 (7.44)                                                                     9.72 (8.80)                                 12   C.sub.10 H.sub.20 N.sub.3 O.sub.5 PS.sub.2                                                 37.79 (37.86) 5.25 (5.41)                                                                     11.02 (11.28)                               13   C.sub.9 H.sub.21 N.sub.2 O.sub.3 PS.sub.2                                                  36.00 (35.59) 7.00 (7.07)                                                                     9.33 (8.80)                                 14   C.sub.8 H.sub.21 N.sub.2 O.sub.3 PS.sub.2                                                  33.33 (32.97) 7.29 (7.44)                                                                     9.72 (8.80)                                 15   C.sub.12 H.sub.21 N.sub.2 O.sub.3 PS.sub.2                                                 44.17 (43.93) 6.44 (6.69)                                                                     8.58 (8.02)                                 16   C.sub.13 H.sub.23 N.sub.2 O.sub.3 PS.sub.2                                                 44.57 (44.67) 6.57 (6.62)                                                                     8.00 (7.68)                                 17   C.sub.10 H.sub.23 N.sub.2 O.sub.3 PS.sub.2                                                 36.36 (34.81) 6.97 (7.75)                                                                     8.48 (8.82)                                 18   C.sub.12 H.sub.27 N.sub.2 O.sub.3 PS.sub.2                                                 35.09 (42.20) 7.89 (7.73)                                                                     8.19 (7.65)                                 19   in test                                                                  20   in test                                                                  ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Numbers are expressed in terms of ppm, δ, relative to                   the standard, tetramethyl silane (TMS).                                       Exam-                                                                         ple                                                                           ______________________________________                                         1: 3.40 (m, 1H, SCH); 3.10 (d, 3H, NCH.sub.3); 3.08 (s, 3H,                      CH.sub.3 SO.sub.2); 2.72 (m, 1H, NH); 2.72 (d of d, 3H, NHCH.sub.3);          1.65 (m, 2H, SCHCH.sub.2); 1.22 [d, 3H, SCH(CH.sub.3)]; 1.0 (t,               3H, SCHCH.sub.2 CH.sub.3).                                                2:  7.57 (m, 4H, C.sub.6 H.sub.4); 3.52 (br s, 1H, NHCH.sub.3); 3.52 (m,          1H,                                                                           SCH); 3.23 (d, 3H, NCH.sub.3); 3.0 (d of d, 3H, NHCH.sub.3); (s,              3H, 4-CH.sub.3 --C.sub.6 H.sub.4); 1.88 (m, 2H SCHCH.sub.2); 1.50 [m,         3H,                                                                           SCH(CH.sub.3)]; 1.0 (t, 3H, SCHCH.sub.2 CH.sub.3).                        3:  5.52 (m, 3H, CH═CH.sub.2), 3.76 (m, 2H, CH.sub.2 CH--CH.sub.2);           3.2 (s,                                                                       3H, CH.sub.3 SO.sub.2); 3.15 (d, 3H, NCH.sub.3); 2.72 (d, 3H,                 NHCH.sub.3);                                                                  2.70 (m, 2H, SCHCH.sub.2); 1.42 [d, 3H, SCH(CH.sub.3)]; 1.0 (t,               3H, SCHCH.sub.2 CH.sub.3).                                                4:  3.55 (br s, 1H, NHCH.sub.3 ; 3.55 (m, 1H, SCH); 3.55 (d, 2H,                  NCH.sub.2 CH.sub.3); 3.10 (s, 3H, CH.sub.3 SO.sub.2); 2.72 (d, 3H,            NHCH.sub.3);                                                                  1.64 (m, 2H, SCH.sub.2 CH.sub.3); 1.40 [d, 3H SCH(CH.sub.3)]; 1.35            (t,                                                                           3H, NCH.sub.2 CH.sub.3); 1.0 (t, 3H, SCHCH.sub.2 CH.sub.3).               5:  3.67 (br s, 1H, NHCH.sub.3); 3.67 (m, 1H, SCH); 3.67 (m, 2H,                  NCH.sub.2); 3.23 (s, 3H, CH.sub.3 SO.sub.2); 2.8 (m, 2H, NCH.sub.2            CH.sub.2); 2.8                                                                (d of d, 3H, NHCH.sub.3); 2.2 (s, 3H, CH.sub.3 S); 1.75 (m, 2H,               SCHCH.sub.2); 1.5 [d, 3H, SCH(CH.sub.3)]; 1.0 (t, 3H, SCHCH.sub.2             CH.sub.3).                                                                6:  4.45 (m, 2H, NCH.sub.2); 3.50 (br s, 1H, NHCH.sub.3); 3.50 (m, 1H,            SCH); 3.33 (s, 3H, CH.sub.3 SO.sub.2); 2.78 (d of d, 3H,                      NHCH.sub.3);                                                                  2.40 (m, 1H, CH.sub.2 C═ CH); 1.65 (m, 2H, SCHCH.sub.2); 1.47             [d,                                                                           3H, SCH(CH.sub.3)]; 1.0 (t, 3H, SCHCH.sub.2 CH.sub.3).                    7:  3.45 (br s, 1H, NHCH.sub.3); 3.45 (m, 1H, SCH); 3.26 (d, 3H,                  NCH.sub.3); 2.75 (d of d, 3H, NHCH.sub.3); 1.65 (m, 2H,                       SCHCH.sub.2);                                                                 1.47 [d, 3H, SCH(CH.sub.3)]; 1.0 (t, 3H, SCHCH.sub.2 CH.sub.3).           8:  3.35 (br s, 1H, NHCH.sub.3); 3.35 (m, 1H, SCH); 3.35 (m, 2H,                  SO.sub.2 CH.sub.2); 3,18 (d, 3H, NCH.sub.3); 2.65 (d of d, 3H,                NHCH.sub.3);                                                                  1.62 (m, 4H, SCHCH.sub.2 and SO.sub.2 CH.sub.2 CH.sub.2); 1.42 [d,            3H,                                                                           SCH(CH.sub.3)]; 1.0 (t, 3H, SCHCH.sub.2 CH.sub.3); 1.0 (m, 2H,                SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3); 0.95 (t, 3H, SO.sub.2          (CH.sub.2)CH.sub.3).                                                      9:  4.25 (br s, 2H, NH.sub.2); 3.40 (m, 1H, SCH); 3.25 (d, 3H,                    NCH.sub.3); 3.22 (s, 1H, CH.sub.3 SO.sub.2); 1.76 (m, 2H, SCHCH.sub.          2); 1.50                                                                      [d, 3H, SCH(CH.sub.3)]; 1.01 (t, 3H, SCHCH.sub.2 CH.sub.3).               10: 7.85 (m, 5H, C.sub.6 H.sub.5); 3.67 (br s, 1H, NHCH.sub.3); 3.35 (m,          1H,                                                                           SCH); 3.15 (d, 3H, NCH.sub.3); 2.70 (m, 3H, NHCH.sub.3); 1.65 (m,             2H, SCHCH.sub.2); 1.50 [d, 3H, SCH(CH.sub.3)]; 1.01 (t, 3H,                   SCHCH.sub.2 CH.sub.3).                                                    11: 3.75 (br s, 1H, NH); 3.40 (m, 1H, SCH); 3.40 (m, 2H,                          SO.sub.2 CH.sub.2); 3.22 (d, 3H, NCH.sub.3); 2.75 (m, 3H,                     NHCH.sub.3); 1.68                                                             (m, 2H, SCHCH.sub.2); 1.42 [d, 3H, SCH(CH.sub.3)]; 1.40 (t, 3H,               SO.sub.2 CH.sub.2 CH.sub.3); 1.00 (t, 3H, SCHCH.sub.2 CH.sub.3).          12: 8.5(q, 4H, C.sub.6 H.sub.4); 3.70 (br s, 1H, NHCH.sub.3); 3.50 (s,            1H,                                                                           SCH); 3.25 (d, 3H, NCH.sub.3); 2.78 (m, 3H, NHCH.sub.3); 1.70 (m,             2H, SCHCH.sub.2); 1.40 [m, 3H, SCH(CH.sub.3)]; 1.00 (t, 3H,                   SCHCH.sub.2 CH.sub.3).                                                    13: 6.02 (m, 1H, NCH.sub.2 CH═CH.sub.2); 5.40 (m, 2H, NCH.sub.2               CH═CH.sub.2);                                                             4.25 (m, 2H, NCH.sub.2 CH═CH.sub.2); 3.25 (s, 3H, CH.sub.3                SO.sub.2); 2.80 (m,                                                           3H, NHCH.sub.3); 1.65 (m, 2H, SCHCH.sub.2); 1.40 (d, 3H,                      SCHCH.sub.3);                                                                 100, (t, 3H, SCHCH.sub.2 CH.sub.3).                                       14: 3.50 (br s, 1H, NHCH.sub.3); 3.50 (m, 1H, SCH); 3.30 (d, 3H,                  NCH.sub.3); 3.25 (s, 1H, CH.sub.3 SO.sub.2); 2.92 (m, 2H,                     NHCH.sub.2); 1.62                                                             (m, 2H, SCHCH.sub.2); 1,40 [d, 3H, SCH(CH.sub.3)]; 1.22 (t, 3H,               NHCH.sub.2 CH.sub.3); 1.00 (t, 3H, SCHCH.sub.2 CH.sub.3).                 15: 7.58 (s, 5H, C.sub.6 H.sub.5); 3.50 (br s, 1H, NHCH.sub.3); 3.50 (m,          1H,                                                                           SCH); 3.32 (s, 1H, CH.sub.3 SO.sub.2); 2.78 (m, 3H, NHCH.sub.3);              1.70                                                                          (m, 2H, SCHCH.sub.2); 1.45 [d, 3H, SCH(CH.sub.3)]; 1.00 (t, 3H,               SCHCH.sub.2 CH.sub.3).                                                    16: 7.40 (m, 5H, C.sub.6 H.sub. 5); 4.80 (d, 2H, CH.sub.2); 3.50 (br S,           1H,                                                                           NHCH.sub.3); 3.50 (m, 1H, SCH); 2.75 (s, 3H, CH.sub.3 SO.sub.2);              2.65                                                                          (m, 3H, NHCH.sub.3); 1.62 (m, 2H, SCHCH.sub.2); 1.40 [d, 3H,                  SCH(CH.sub.3)]; 1.00 (t, 3H, SCHCH.sub.2 CH.sub.3).                       17: 3.90 (m, 4H, NCH.sub.2 CH.sub.2); 3.50 (br S, 1H, NHCH.sub.3); 3.50           (m,                                                                           1H, SCH); 3.42 (s, 3H, CH.sub.3 O); 3.35 (s, 3H, CH.sub.3 SO.sub.2);          2.78                                                                          (m, 3H, NHCH.sub.3); 1.62 (m, 2H, SCHCH.sub.2); 1.40 [d, 3H,                  SCH(CH.sub.3)]; 1.00 (t, 3H, SCHCH.sub.2 CH.sub.3).                       18: 4.1 [m, 1H, N--CH(CH.sub.2).sub.5 ]; 3.50 (br S, 1H, NHCH.sub.3);             3.50                                                                          (m, SCH); 3.18 (s, 3H, CH.sub.3 SO.sub.2); 2.75 (m, 3H, NHCH.sub.3);          1.62 (m, 2H, SCHCH.sub.2); 1.62 (m, 2H, SCHCH.sub.2); 1.50 [br m,             10H, (CH.sub.2).sub.5 ]; 1.40 [d, 3H, SCH(CH.sub.3)]; 1.00 (t, 3H,            SCHCH.sub. 2 CH.sub.3).                                                   19: 4.20 Im, 1H, OCH); 3.50 (br S, 1H, NHCH.sub.3); 3.50 (m, 1H,                  SCH); 3.22 (d, 3H, NCH.sub.3); 2.78 (m, 3H, NHCH.sub.3); 1.65 (m,             2H, SCHCH.sub.2); 1.42 [d, 6H, OCH(CH.sub.3).sub.2 ]; 1.42 [d, 3H,            SCH(CH.sub.3)]; 1.00 It, 3H, SCHCH.sub.2 CH.sub.3).                       20: 7.65 (m, 4H, C.sub.6 H.sub.4); 4.00 (s, 3H, CH.sub.3 O); 3.50 (br S,          1H,                                                                           NHCH.sub.3); 3.50 (m, 1H, SCH); 3.18 (d, 3H, NCH.sub.3); 2.80 (m,             3H, NHCH.sub.3); 1.70 (m, 2H, SCHCH.sub.2); 1.40 [m, 3H,                      SCH(CH.sub.3)]; 1.00 (t, 3H, SCHCH.sub.2 CH.sub.3).                       ______________________________________                                    

Biological Section

Initial evaluations were made on the following mite, insect, andnematode:

    ______________________________________                                        Code Symbol Common Name    Latin Name                                         ______________________________________                                        TSM         Two-spotted spider                                                                           Tetranychus                                                    mite           urticae                                            SAW         Southern armyworm                                                                            Spodoptera                                                                    eridania                                           nema        Southern root-knot                                                                           Meloidogyne                                                    nematode       incognita                                          ______________________________________                                    

A test solution containing 600 ppm of test compound was made bydissolving the test compound in a solvent (acetone:methanol, 1:1),adding surfactant and then water to give an acetone:methanol:watersystem of 10:10:80. A 1:1 mixture of an alkylarylpolyetheralcohol(commercially available under the trademark Triton X-155) and a modifiedphthalic glycerol alkyl resin (commercially available under thetrademark Triton B-1956) were utilized at the equivalent of one ounceper 100 gallons of test solution and a surfactant.

For the mite test, infested bean (Phaseolus limeanus) leaf discs (1.25inches in diameter) containing about 50 mites were placed in a Petridish lid on a moistened piece of cotton. The leaves were then sprayedwith the test solution using a rotating turntable. They were held for 24hours and then the percent kill was determined.

For the armyworm test, detached bean leaves on pieces of moistenedfilter paper were sprayed as above for the mite test in similar dishesand allowed to dry. The dishes were infested with 10 third instarsouthern armyworm larvae. The dishes were covered. After holding for 48hours, the percent kill was obtained.

For the nematode test, soil was homogeneously inoculated with amacerated blend of tomato roots heavily knotted with the root knotnematode. Ten milliliters of the test soil were added to 200 millilitersof the inoculated soil in a 16 oz. jar to give a concentration by volumeof about 30 ppm. The jar was then shaken to insure thorough mixing,immediately uncapped, and allowed to air for 24 hours. The soil was thenplaced into a 3 inch plastic pot after which time 3 cucumber (Cucumissativus) seeds were planted. About 23 days thereafter, the cucumberplants were removed from the soil and the root system examined for thepresence of knots. A total of 15 knots or less was considered a measureof control.

Table IV gives the results of the foregoing biological evaluations.

                  TABLE IV                                                        ______________________________________                                        Biological Evaluation Results                                                 Ex. No.                                                                              Two-Spotted Mite                                                                            Southern Armyworm                                                                            Nema*                                     ______________________________________                                        1      100           100            +                                         2      100           100            +                                         3      100           100            +                                         4      100           100            +                                         5      100           100            +                                         6      100           100            +                                         7      100           100            +                                         8      100           100            +                                         ______________________________________                                         *+ means control, 15 knots or less, at 150 ppm.                          

What is claimed is:
 1. A compound having the formula: ##STR8## R¹ isunsubstituted or substituted C₁ -C₆ alkyl wherein the substituent can befrom one to three of the same or different halogens selected from Cl,Br, or F groups;C₃ -C₈ cycloalkyl; unsubstituted or substituted phenylor naphthyl, or can be one to three of the same or differentsubstituents selected from cyano, nitro, halo, alkyl, alkoxy, alkylthio,alkylsulfinyl, alkylsulfonyl, phenoxy, haloalkyl, mono- ordi-alkylamino, mono- or di-alkylaminocarbonyl, alkoxy-carbonyl,alkylcarbonyl, alkylcarbonyloxy, phenylthio, phenylsulfinyl,phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl,phenylcarbonyloxy, phenylaminocarbonyl, alkenyloxycarbonyl,alkenylcarbonyloxy, aminocarbonyl, or alkylcarbonylamino and the likewherein the alkyl moiety thereof is a straight or branched chain groupcontaining one to six carbon atoms; R² is hydrogen;unsubstituted orsubstituted C₁ -C₆ alkyl wherein the substituent can be a halo, cyano,alkoxy, alkylthio, alkylcarbonyl, alkoxy-carbonyl, alkoxycarbonyloxy,mono- or di-alkylamino, phenoxy or phenylthio groups; C₃ -C₈ cycloalkyl;C₃ -C₆ alkenyl; unsubstituted or substituted phenyl or naphthyl, orunsubstituted or substituted phenyl(C₁ -C₅)alkyl, wherein thesubstituent on the phenyl or naphthyl ring can be one to three of thesame or different substituents selected from cyano, nitro, halo, alkyl,alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, phenoxy, haloalkyl,mono- or di-alkylamino, mono- or di-alkylaminocarbonyl, alkoxycarbonyl,alkylcarbonyl, alkylcarbonyloxy, phenylthio, phenylsulfinyl,phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl,phenylcarbonyloxyl, phenylaminocarbonyl, alkenyloxycarbonyl,alkenylcabonyloxy, aminocarbonyl, or alkylcarbonylamino and the likewherein the alkyl moiety thereof is a straight or branched chain groupcontaining one to six carbon atoms; C₃ -C₆ alkynyl; R³ is hydrogen,methyl or ethyl; R⁴ is hydrogen, methyl, C₁ -C₆ alkylthio(C₁ -C₂)alkyl,C₁ -C₆ alkoxy(C₁ -C₂)alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl; R⁵ is C₂ -C₆alkyl; and X is O or S.
 2. A compound according to claim 1 wherein X isO.
 3. A compound according to claim 2 whereinR¹ is an unsubstituted orsubstituted C₁ -C₆ alkyl group wherein the substituent can be from oneto three of the same or different halogens selected from chloro, bromoor fluoro groups; R² is an unsubstituted or substituted C₁ -C₆ alkylgroup wherein the substituent can be a cyano, alkoxy, alkylthio,alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, mono- or di-alkylamino,phenoxy or phenylthio group;a C₃ -C₆ alkenyl group; or a C₃ -C₆ alkynylgroup; R³ is a methyl group; R⁴ is hydrogen, methyl, C₃ -C₄ alkenyl;C₃-C₄ alkynyl; R⁵ is C₂ -C₆ alkyl; and X is O.
 4. A compound according toclaim 3 whereinR¹ is an unsubstituted or substituted C₁ -C₆ alkyl groupwherein the substituent can be one to three of the same or differenthalogens selected from chloro, bromo or fluoro groups; R² is anunsubstituted C₁ -C₃ alkyl group;a C₃ -alkenyl group; or a C₃ -alkynylgroup; R³ is methyl; R⁴ is hydrogen; R⁵ is 1-methylpropyl; and X is O.5. A compound according to claim 4 wherein R¹ is methyl; R² is methyl;R³ is methyl; R⁴ is hydrogen; and R⁵ is 1-methylpropyl.
 6. A compoundaccording to claim 4 wherein R¹ is 4-methyl-phenyl; R² is methyl; R³ ismethyl; R⁴ is hydrogen; and R⁵ is 1-methylpropyl.
 7. A compoundaccording to claim 3 wherein R¹ is methyl; R² is methyl; R³ is methyl;R⁴ is 2-propenyl; and R⁵ is 1-methylpropyl.
 8. A compound according toclaim 4 wherein R¹ is methyl; R² is ethyl; R³ is methyl; R⁴ is hydrogen;and R⁵ is 1-methylpropyl.
 9. A compound according to claim 4 wherein R¹is methyl; R² is methylthioethyl; R³ is methyl; R⁴ is hydrogen; and R⁵is 1-methylpropyl.
 10. A compound according to claim 4 wherein R¹ ismethyl; R² is 2-propynyl; R³ is methyl; R⁴ is hydrogen; and R⁵ is1-methylpropyl.
 11. A compound according to claim 4 wherein R¹ istrifluoromethyl; R² is methyl; R³ is methyl; R⁴ is hydrogen; and R⁵ is1-methylpropyl.
 12. A compound according to claim 4 wherein R¹ isn-butyl; R² is methyl; R³ is methyl; R⁴ is hydrogen; and R⁵ is1-methylpropyl.
 13. A method of controlling pests comprising contactingthe pests with a pesticidally effective amount of a compound accordingto claim
 1. 14. A method of controlling pests comprising contacting thepests with a pesticidally effective amount of a compound according toclaim
 4. 15. A pesticidal composition comprising a pesticidallyeffective amount of a compound according to claim 1 and an agronomicallyacceptable carrier.
 16. A pesticidal composition comprising apesticidally effective amount of a compound according to claim 4 and anagronomically effective carrier.